Abstract
The reaction of aniline with hydrogen atom is investigated herein using the hybrid meta-DFT functional of BB1 K. Hydrogen atom is found to preferentially add at an ortho position. However, the fate of the o-(C6H5NH2)H adduct is found to be solely the deactivation of the initial addition channel. The rate constant for the abstraction channel (C6H5NH2 + H → C6H5NH + H2) is fitted by the expression 1.10 × 10-11 exp(-4,200/T) cm3 molecule-1 s-1. Our calculated rate constant for the abstraction channel agrees very well with the available experimental measurements. Satisfactory agreement is found between calculated and experimental measurements for the displacement channel (C6H5NH2 + H → C6H6 + NH2). Our detailed analysis for the corresponding displacements in toluene and phenol suggests that the three systems exhibit similar behavior with regard to the relative importance of abstraction and displacement channels.
Original language | English |
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Pages (from-to) | 823-832 |
Number of pages | 10 |
Journal | Theoretical Chemistry Accounts |
Volume | 129 |
Issue number | 6 |
DOIs | |
Publication status | Published - Aug 2011 |
Externally published | Yes |
Keywords
- Abstraction vs. displacement
- Aniline
- H atoms
- Hybrid meta-DFT
- Reaction rate constant
ASJC Scopus subject areas
- Physical and Theoretical Chemistry